TWI644939B - Varnish,prepreg,film having resin,metallic foil-clad laminate and print circuit board - Google Patents

Abstract

The present invention provides a varnish obtained by reacting at least a part of the above functional group of a resin having a functional group reactive with an amine group and containing a polycyclic structure, and a compound having a compound having an amine group in a solvent, and having A varnish obtained by reacting at least a part of the above-mentioned functional group of a resin having a polycyclic structure with a functional group having a polycyclic structure and reacting the phenolic hydroxyl group of a compound having a phenolic hydroxyl group in a solvent. Further, the present invention provides a prepreg obtained by using any one of the varnishes, a resin film, a metal foil-clad laminate, and a printed circuit board.

Description

Varnish, prepreg, resin film, metal foil laminate, and printed circuit board

The present invention relates to a varnish used in the production of a laminated board and a printed circuit board used in an electronic device, and a prepreg prepared by using the varnish, a resin film, a metal foil laminated board, and a printed circuit board. .

In recent years, electronic devices are being reduced in size and weight, and high-density wiring such as thin multilayering or fine wiring is required for the printed circuit board of the electronic device. In order to realize high-density wiring, the printed circuit board is required to have a low thermal expansion rate for the purpose of improving the reliability of the fine wiring on the substrate. In particular, in a package substrate application of a high-density printed circuit board in which a semiconductor device such as a semiconductor wafer is packaged, the required characteristics are more stringent than those of the core substrate or the like.

Further, regarding the packaging method, a flip chip connection method has been widely used instead of the previous wire bonding method. The flip chip connection method is a method in which a circuit board is connected to a semiconductor device and soldered by a solder ball instead of a wire used in the wire bonding method. The semiconductor package using the package method may be a chip scale package (CSP), a package on package (PoP), and a system in package (SiP).

When the solder balls are connected, the solder balls and the board are heated to about 300 ° C during reflow. The circuit board is usually made of a prepreg formed of a resin composition, a fiber base material or a support, or a laminated board obtained by laminating a resin film and a metal foil, and forming a wiring from a metal foil. Therefore, there is a problem in that the board expands due to heat, and strain, particularly stress, of the substrate called warpage is generated due to the difference in thermal expansion ratio between the packaged electronic parts (especially the semiconductor device) and the resin of the board. Focusing on the solder balls located at the connection portion between the semiconductor device and the circuit board causes cracks to cause connection failure.

The warpage of the semiconductor package of the PoP structure will be specifically described using FIG. First, the semiconductor package is provided with the following circuit board via the solder balls 22 on the substrate 18, that is, the semiconductor wafer 10 electrically connected by the bonding wires 14 is mounted on the semiconductor package substrate 16 on which the through holes 20 are formed, and It is sealed with a sealant 12 thereon. When the board is heated in this state, warpage occurs due to a difference in thermal expansion coefficient between the sealing material 12 and the wafer 10 and the semiconductor package substrate 16, and cracks C are generated.

Against this background, a laminated board which is less prone to warpage and has a low coefficient of thermal expansion is sought. The conventional laminated board is usually a laminated board in which a resin composition containing an epoxy resin as a main component is impregnated into a glass woven fabric or a non-woven fabric and dried to form a prepreg, and the prepreg is superposed on a plurality of sheets. Further, a metal foil is provided on one or both sides and heated and pressurized. The epoxy resin is excellent in balance of insulation, heat resistance, cost, and the like, but has a large thermal expansion coefficient. Therefore, for example, as disclosed in Patent Document 1, an inorganic filler such as cerium oxide is added to lower the coefficient of thermal expansion of the resin composition.

Further high thermal expansion rate can be achieved by filling a large amount of inorganic filler. However, due to moisture absorption due to the inorganic filler, deterioration in insulation reliability, poor adhesion of the resin-wiring layer, deterioration of drilling processability, etc., high filling in the use of a multilayer circuit board or a package substrate exists. limit.

Further, Patent Document 2 and Patent Document 3 disclose a method of increasing the crosslinking density of a resin composition, increasing Tg, and lowering the coefficient of thermal expansion. However, increasing the crosslink density shortens the molecular chain between crosslinks and has a limit in terms of reactivity or resin structure.

On the other hand, Patent Document 4 discloses the following method as an effective method for lowering the coefficient of thermal expansion, that is, an epoxy resin having a polycyclic structure in which the molecular weight between crosslinking points is made appropriate. However, the prior epoxy resin having a polycyclic structure is crystallized due to the mutual attraction of the intermolecular forces of the polycyclic structural moiety, so that the solubility in a solvent is low, even if it is dissolved in an organic solvent by heating. If it returns to normal temperature, it will crystallize again.

Further, Patent Document 5 discloses a method of using a resin having a polycyclic structure as an effective method for achieving low warpage. Patent Document 5 describes that a resin containing a polycyclic structure is effective for use in a sealing material. In the case of the use of the sealing material, it is not necessary to form a varnish, and there is no problem of recrystallization when dissolved in an organic solvent.

However, when the development in laminated board use is studied, as described above, the resin containing a polycyclic structure is extremely insoluble in an organic solvent, and the storage stability at room temperature in a state where a varnish is made is poor. It must be dissolved in a solvent before the laminate is prepared to make a varnish.

Therefore, as long as the storage stability at room temperature of the resin containing a polycyclic structure can be improved, the workability at the time of using a varnish is industrially significant.

Prior technical literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2004-182851

Patent Document 2: Japanese Patent Laid-Open Publication No. 2000-243864

Patent Document 3: Japanese Patent Laid-Open Publication No. 2000-114727

Patent Document 4: Japanese Patent Laid-Open Publication No. 2007-314782

Patent Document 5: Japanese Patent Laid-Open Publication No. 2007-002110

An object of the present invention is to provide a varnish having high storage stability at normal temperature and excellent workability at the time of use, and a prepreg, a resin film, a metal foil-clad laminate, and a printed circuit board formed using the varnish. .

The inventors of the present invention have diligently studied in order to achieve the above object, and as a result, have conceived the following invention. The invention is as follows.

[1] A varnish obtained by reacting a part of the above functional group of a resin having a polycyclic structure with a functional group reactive with an amine group and a compound having an amine group based on a solvent.

[2] The varnish according to [1], wherein the varnish is a part of the functional group of a resin having a polycyclic structure and having a functional group having a polycyclic structure, and a compound having a phenolic hydroxyl group; The phenolic hydroxyl group is reacted in the above solvent.

[3] The varnish according to [1] or [2] wherein the compound having an amine group is guanamine, dicyandiamide, and amino triazine novolac. Any of them.

[4] A varnish in which a part of the above-mentioned functional group of a resin having a polycyclic structure having a functional group reactive with a phenolic hydroxyl group is reacted with a phenolic hydroxyl group of a compound having a phenolic hydroxyl group in a solvent obtain.

[5] The varnish according to [2] or [4] wherein the compound having a phenolic hydroxyl group is a phenol novolac resin or a cresol novolak resin.

[6] The varnish according to any one of [1] to [5] wherein the resin contains at least one epoxy group as the functional group.

[7] The varnish according to any one of [1] to [6] wherein the resin has a group selected from the group consisting of a biphenyl structure, a naphthalene structure, a biphenol novolak structure, an anthracene structure, and an indoline structure. At least one of the groups.

[8] A varnish containing a resin component having a structure represented by the following formula (1),

[Chemical 1]

(In the above formula, R ¹ is a residue of a compound having an amine group).

[9] The varnish according to the above [8], wherein the total ratio of the respective structures of the structure represented by the above formula (1) and the structure represented by the following formula (2) is represented by the above formula (1) The existence ratio of the structure is 40% or less.

[Chemical 2]

[10] A prepreg obtained by applying the varnish according to any one of [1] to [9] to a substrate and heating and drying the varnish.

[11] The prepreg according to [10], wherein the substrate is a glass woven fabric, a glass nonwoven fabric, an aromatic polyamide woven fabric or an aromatic polyamide woven nonwoven fabric.

[12] A resin film obtained by applying the varnish according to any one of [1] to [9] onto a film and heating and drying the film.

[13] A metal foil-clad laminate having a conductor layer on at least one surface of the prepreg as described in [10] or [11].

[14] A metal foil-clad laminate having a conductor layer on at least one surface of the resin film as described in [12].

[15] A printed circuit board formed by wiring the conductor layer provided on at least one surface of the metal foil-clad laminate according to [13] or [14].

[Effects of the Invention]

According to the present invention, it is possible to provide a varnish having high storage stability at normal temperature and excellent workability at the time of use, and a prepreg, a resin film, a metal foil-clad laminate, and a printed circuit board formed using the varnish. .

The above and other objects, features and advantages of the present invention will become more <RTIgt;

[1] Varnish:

The first varnish of the present invention is obtained by reacting at least a part of a functional group of a resin having a polycyclic structure with a functional group reactive with an amine group, and a compound having a compound having an amine group, based on a solvent.

The first varnish of the present invention may be referred to as a varnish containing a resin component having a structure represented by the following formula (1).

[Chemical 3]

In the above formula, R ¹ is a residue of a compound having an amine group. Regarding the compound having an amine group, it will be described below.

Further, the second varnish of the present invention is a reaction of at least a part of a functional group of a resin having a polycyclic structure with a functional group reactive with a phenolic hydroxyl group, and a phenolic hydroxyl group of a compound having a phenolic hydroxyl group in a solvent. And the varnish obtained. The compound having a phenolic hydroxyl group will be described below.

In the present specification, the "resin having a polycyclic structure having a functional group reactive with an amine group" and "a resin having a polycyclic structure having a functional group reactive with a phenolic hydroxyl group" are appropriately referred to as " A resin containing a polycyclic structure."

The first varnish and the second varnish of the present invention (hereinafter, the varnish may be simply referred to as "the varnish of the present invention") are a resin containing a polycyclic structure and a compound having an amine group or having a phenolic hydroxyl group. After the compound is dispersed in a solvent, the reaction is carried out by heating or the like, and the solvent solubility of the resin having a polycyclic structure is improved, and the resin can be stored for a long period of time. In addition, since it is not necessary to contain an additive or the like for improving solubility, the deterioration of the resin property is small, and it is excellent in the property maintenance.

Hereinafter, the varnish of the present invention will be described in detail.

(resin containing multi-ring structure)

The "polycyclic structure" of the resin having a polycyclic structure of the present invention means a structure in which aromatic rings are bonded to each other via a single bond or a structure in which an aromatic ring is condensed.

Examples of the structure in which the aromatic rings are bonded to each other via a single bond include a biphenyl structure, a biphenol novolak structure, and a terphenyl structure.

Further, examples of the structure in which the aromatic ring is condensed include a naphthalene structure, a naphthol novolak structure, a fluorene structure, a dihydroanthracene structure, a phenanthrene structure, a tetracene structure, a chrysene structure, and a ternary benzene. Structure, tetraphene structure, pyrene structure, picene structure, and perylene structure.

The structure as described above may be used singly or in combination of two or more. The biphenyl structure, the biphenyl aldehyde varnish structure, and the naphthalene structure are preferable in terms of characteristics (thermal expansion property, heat resistance, and the like) of the laminated board, the printed circuit board, the package substrate, and the like which are formed by using the varnish of the present invention. The naphthol novolak structure, the fluorene structure and the dihydroanthracene structure are more preferably a biphenyl structure, a biphenyl aldehyde varnish structure, a naphthalene structure, an anthracene structure or an indoline structure. These structures are preferable because they can easily exhibit a stacking feature because the three-dimensional structure is fixed.

The resin containing a polycyclic structure is preferably a thermosetting resin from the viewpoint of high fluidity at the time of heating, heat resistance after curing, and dimensional stability. The thermosetting resin may, for example, be an epoxy resin or a cyanate resin, and is preferably an epoxy resin from the viewpoint of productivity and workability.

Further, in the case of an epoxy resin, a functional group reactive with an amine group and a functional group reactive with a phenolic hydroxyl group are epoxy groups.

Among the above-mentioned epoxy resins, a naphthol novolak type epoxy resin or a biphenyl novolak type epoxy resin is preferable from the viewpoint of moldability, and a naphthalene type epoxy is preferable from the viewpoint of low thermal expansion property. Resin, bismuth type epoxy resin, indoline type epoxy resin. These resins may be used singly or in combination of two or more. In order to exhibit the properties of the resins, it is preferred to use the resins in an amount of 30% by weight or more based on the total amount of the epoxy resins, more preferably 50% by weight or more. .

Specific examples of preferred epoxy resins are shown below.

The biphenyl novolak type epoxy resin is preferably an epoxy resin represented by the following formula (3). The epoxy resin having the structure represented by the formula (3) can be obtained, for example, as NC-3000 (manufactured by Nippon Kayaku Co., Ltd.) as a commercial product.

[Chemical 4]

In the above formula, R ⁴ to R ^{7 are the} same or different from each other and represent hydrogen or an alkyl group.

Further, n is a number satisfying n &gt; 0, preferably 1.5 ≦ n ≦ 4.0.

The naphthol novolak type epoxy resin is preferably an epoxy resin having a structure represented by the following formula (4). For the epoxy resin having the structure represented by the formula (4), for example, ESN-175 (manufactured by Tohto Kasei Co., Ltd.), which is a commercially available product, can be obtained.

[Chemical 5]

m in the above formula is a number satisfying m &gt; 0, preferably 2 ≦ m ≦ 7.

The dihydroanthracene type epoxy resin is preferably an epoxy resin having a structure represented by the following formula (5). The epoxy resin having the structure represented by the formula (5) can be obtained, for example, as YX-8800 (manufactured by Nippon Epoxy Resin Co., Ltd.) as a commercial product.

[Chemical 6]

In the above formula, R ⁸ and R ^{9 are the} same or different from each other, and represent an alkyl group having 4 or less carbon atoms. x represents an integer from 0 to 4, and y represents an integer from 0 to 6.)

The fluorene type epoxy resin is preferably an epoxy resin having a structure represented by the following formula (6).

[Chemistry 7]

In the formula, R ¹⁴ to R ¹⁷ are the same as R ⁴ to R ⁷ in the formula (3).

(compound with amine group)

The amine group-containing compound of the present invention may have at least one or more amine groups in the molecule, for example, "reactive group equivalent of a compound having an amine group": "a ring of an epoxy resin having a polycyclic structure" The heat generation start temperature when the oxygen equivalent is 1:1 is preferably 60° C. or higher and 200° C. or lower, more preferably 70° C. or higher and 190° C. or lower, and further preferably 80° C. or higher and 180° C. or lower. When the heat generation start temperature is within the range of the heat generation start temperature, the hardening reaction at normal temperature does not proceed rapidly, so that the storage stability (storage stability) is improved.

The measurement of the onset temperature of the heat generation can be measured by a differential scanning calorimetry (DSC) measurement. Specifically, in Fig. 2 (DSC curve for YX-8800 and dicyandiamide in an equivalent ratio of 1:1), it can be obtained from the rising point of the curve (point A in Fig. 2).

Examples of the compound having an amine group include guanidine amine, acetoguanamine, guanoguanamine, and the like, or a guanamine resin derived from the guanamine, dicyandiamide. An amine, melamine or a melamine resin derived from the melamine, a triethylenetetramine, an aminotriazine novolak resin or the like. The molecular weight of these compounds is preferably 60 or more, more preferably 80 or more. When such a molecular weight is bonded to a resin having a polycyclic structure by a reaction of a compound having an amine group, it can be sufficiently large to prevent crystallization of a resin having a polycyclic structure. Further, several compounds having an amine group may also be used in combination. Among these compounds, benzoguanamine, dicyandiamide, and an aminotriazine novolak resin are preferable from the viewpoint of thermal expansion property, heat resistance, reliability, and the like after the formation of the laminated sheet.

Further, examples of the residue of the compound having R ¹ in the formula (1), that is, the residue of the above-exemplified resin or compound.

(compound with phenolic hydroxyl group)

The compound having a phenolic hydroxyl group used in the present invention may have one or more hydroxyl groups in the molecule, and more preferably two or more from the viewpoint of crosslinking. For example, naphthalenediol, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, aminotriazine novolak resin, and amine group containing bis-xetylenediamine may be mentioned. Triazine novolak resin, bisphenol A, bisphenol F, and the like. Among them, a phenol novolak resin and a cresol novolak resin are preferable. The molecular weight of these compounds is not particularly limited, and several kinds may be used in combination.

Here, the reaction group equivalent of the "phenolic hydroxyl group-containing compound" is set to "the epoxy equivalent of the epoxy resin having a polycyclic structure" = 1:1, and the heat generation start temperature is preferably 60 ° C or more and 200. Below °C, it is more preferably 70 ° C or more and 190 ° C or less, and particularly preferably 80 ° C or more and 180 ° C or less. When the heat generation start temperature is within the range of the heat generation start temperature, the hardening reaction at normal temperature does not proceed rapidly, so that the storage stability (storage stability) is improved.

Further, when a compound having a phenolic hydroxyl group is used, a curing accelerator described later is used in combination.

Further, a compound having a phenolic hydroxyl group may be used in combination with a compound having an amine group in a reaction in a solvent. In this case, the compound having a phenolic hydroxyl group is preferably set to 0.01 equivalent to 100 equivalents, more preferably 0.03 equivalent to 30 equivalents, per equivalent of the compound having an amine group. By setting the amount to 0.05 equivalent to 20 equivalents, a compound having a phenolic hydroxyl group and a compound having an amine group can be efficiently reacted with a thermosetting resin.

Here, the reaction group equivalent of "a compound having a phenolic hydroxyl group and a compound having an amine group" is set: "the epoxy equivalent of the epoxy resin having a polycyclic structure" = 1:1 is preferable. It is 60° C. or higher and 200° C. or lower, more preferably 70° C. or higher and 190° C. or lower, and particularly preferably 80° C. or higher and 180° C. or lower. When the heat generation start temperature is within the range of the heat generation start temperature, the hardening reaction at normal temperature does not proceed rapidly, and the storage stability (storage stability) is improved.

(resin component having a structure represented by formula (1))

The resin component having the structure represented by the formula (1) of the present invention can be obtained by reacting the above epoxy resin having a polycyclic structure with a compound having an amine group in a solvent. Specifically, at least a part of the epoxy group of the epoxy resin reacts with an amine group of the compound having an amine group, and a resin component having a structure represented by the formula (1) can be obtained.

An example of the structure represented by the formula (1) of the present invention is shown below.

First, the resin component obtained from the biphenyl novolak type epoxy resin represented by the formula (3) and the compound having an amine group has a structure represented by the following formula (7).

[化8]

In the above formula, R ^{1 is the} same as in the formula (1) (the same applies hereinafter). o is a number satisfying o > 0, and p is a number satisfying p > 0.

In addition, the resin component obtained from the naphthol novolak type epoxy resin represented by the formula (4) and the compound having an amine group has a structure represented by the following formula (8).

[Chemistry 9]

In the above formula, q is a number satisfying q>0, and r is a number satisfying r>0.

The resin component obtained from the indoline type epoxy resin represented by the formula (5) and the compound having an amine group contains a compound having a structure represented by the following formula (9).

[化10]

In the above formulas, R ₈ and R _9, x and y of the formula R ₈ and R ₉ (5) in the same x and y.

In the varnish of the present invention, the ratio of the presence of the resin component represented by the above formula (1) to the total ratio of the respective ratios of the structures represented by the formula (1) and the structure represented by the following formula (2) It is preferably 40% or less, more preferably 5% or more and 40% or less. Further, it is preferably 8% or more and 40% or less, and particularly preferably 10% or more and 35% or less.

When the ratio of the resin component represented by the above formula (1) is 40% or less, the compound having an amine group added by modification prevents the molecular arrangement of the epoxy resin having a polycyclic structure and crystallizes Therefore, the varnish having good storage stability can be obtained without crystallization again.

In addition, when it exceeds 40%, a hardening reaction may occur and storage stability may be inadequate.

[11]

The ratio of the epoxy resin having a polycyclic structure in the present invention to the compound having an amine group and/or the compound having a phenolic hydroxyl group at the time of reaction, relative to the epoxy equivalent of the epoxy resin, the compound having an amine group The hydroxyl group equivalent of the amine group and/or the hydroxyl group having a phenolic hydroxyl group is preferably in the range of 0.05 to 20, more preferably in the range of 0.10 to 10, and particularly preferably 0.20 to 5. When it is 0.05 to 20 with respect to the epoxy equivalent of the epoxy resin, the dissolution effect of the epoxy resin having a polycyclic structure is not lacking, and workability is good. Further, by being within the above range and the existence ratio of the formula (1) and the formula (2) is within the above-described range, the synthesis time can be shortened and the storage stability can be improved.

Further, the varnish of the present invention may have a structure of the following formula (10) in the resin component.

[化12]

When the structure represented by the above formula (10) is contained, the ratio of the existence of the structure represented by the formula (1) in the resin component, the ratio of the existence of the structure represented by the formula (2), and the formula (10) The total ratio of the existence ratios of the structures, the total ratio of the ratios of the structures represented by the formulas (1) and (10) is preferably 40% or less, more preferably 1% or more and 40% or less. Further, it is preferably 5% or more and 35% or less, and particularly preferably 10% or more and 30% or less.

When the total ratio of the ratios of the structures represented by the formulas (1) and (10) is 40% or less, the compound having an amine group added by modification is prevented from having an epoxy resin having a polycyclic structure. The molecules are aligned and crystallized, and the varnish having good storage stability can be obtained without being crystallized again.

In addition, when it exceeds 40%, a hardening reaction may occur and storage stability may become inadequate.

Further, the varnish is prepared by adjusting the equivalent ratio of the reactive group of the epoxy group: curing agent to 0.8 to 1.2, and the properties after curing are improved.

In order to mix an epoxy resin having a polycyclic structure with a compound having an amine group and/or a compound having a phenolic hydroxyl group, a solvent is preferably added.

The solvent may be any solvent, especially acetone, if the epoxy resin having a polycyclic structure is reacted with a compound having an amine group and a compound having a phenolic hydroxyl group and the solvent-free resin composition is soluble. , methyl ethyl ketone, methyl butyl ketone, toluene, xylene, ethyl acetate, N, N-dimethylformamide, N,N-dimethylacetamide, ethanol, ethylene glycol Methyl ether, propylene glycol monomethyl ether acetate, etc. are excellent in solubility and are preferable. In particular, propylene glycol monomethyl ether is preferred from the viewpoint of dissolving a resin having high crystallinity.

The amount of the solvent to be prepared is such that a solvent-free resin composition obtained by reacting an epoxy resin having a polycyclic structure with a compound having an amine group and a compound having a phenolic hydroxyl group is soluble. The total amount of the resin component obtained by reacting the epoxy resin having a polycyclic structure with a compound having an amine group and a compound having a phenolic hydroxyl group is preferably 5 parts by weight to 300 parts by weight. The range of parts is more preferably in the range of 30 parts by weight to 200 parts by weight. Further, the above solvents may be used in combination.

The weight average molecular weight of the resin component after the reaction of the present invention is preferably 800 or more and 4,000 or less, more preferably 900 or more and 3,500 or less, and still more preferably 950 or more and 3,000 or less. The weight average molecular weight of the compound in the varnish can be determined, for example, by GPC (measurement using a calibration curve of standard polystyrene obtained by gel permeation chromatography). When the weight average molecular weight of the compound in the varnish is in the above range, crystals are not precipitated, and a varnish having excellent handleability in which the solubility of the resin having a polycyclic structure is improved is formed.

The varnish of the present invention may contain a resin or a hardener as needed in the above components. The curing agent is not particularly limited as long as it has a curing action of the thermosetting resin, and examples thereof include acid anhydrides such as maleic anhydride and maleic anhydride copolymer, phenol novolac, cresol novolac, and amine group. A phenol compound such as a triazine novolak resin. The hardener may be used singly or in combination of two or more.

In the varnish of the present invention, a hardening accelerator may be contained in the production of the laminated board. Examples of the hardening accelerator include imidazoles and derivatives thereof, tertiary amines, and quaternary ammonium salts.

Further, in the varnish of the present invention, other components may be blended as needed within a range that does not impair the effects of the present invention.

Examples of other components include flame retardants such as an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyfluorene-based flame retardant, and a metal hydroxide; cerium powder, nylon powder, and fluorine powder; Organic fillers such as Orben, Bentone, etc., antimony-based, anti-foaming agents or homogenizing agents; antimony-based, thiazole-based, triazole-based, decane-based coupling agents, etc. Adhesive imparting agent; ultraviolet absorber such as benzotriazole; antioxidant such as hindered phenol or styrenated phenol; benzophenone, benzil ketal; thioxanthone a photopolymerization initiator such as thioxanthone), a fluorescent whitening agent such as a stilbene derivative; phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow ), a coloring agent such as carbon black, and the like.

Further, in order to impart low thermal expansion rate or flame retardancy, an inorganic filler or an additive may be added within a range that does not impair the effects of the present invention. As the inorganic filler, cerium oxide, aluminum oxide, aluminum hydroxide, calcium carbonate, clay, talc, tantalum nitride, boron nitride, titanium oxide, barium titanate, lead titanate, barium titanate or the like can be used. When the blending amount is 300 parts by weight or less, preferably 200 parts by weight or less, based on 100 parts by weight of the total amount of the solvent-free resin component of the present invention, the material for a multilayer wiring board of the present invention is uniform and obtained. Good operability, so it is better.

In particular, when the resin containing a polycyclic structure of the present invention is used, the inorganic filler serves as a "crystal nucleus" for promoting crystallization, so care must be taken when mixing a large amount. As the additive, various decane coupling agents, hardening accelerators, antifoaming agents and the like can be used. The amount of the resin composition is preferably 5 parts by weight or less based on 100 parts by weight of the total amount of the solvent-free resin component, and more preferably 3 parts by weight or less from the viewpoint of maintaining the properties of the resin composition. In order to uniformly disperse the inorganic filler, it is effective to use a masher, a homogenizer or the like.

The reaction of the polycyclic structure-containing resin of the present invention with a compound having an amine group and/or a compound having a phenolic hydroxyl group is preferably carried out at 80 ° C or higher and 250 ° C or lower, more preferably 85 ° C or higher and 245 ° C. Hereinafter, it is preferably 90° C. or higher and 240° C. or lower.

In addition, the reaction time is preferably 10 minutes or longer and 30 hours or shorter, more preferably 30 minutes or longer and 20 hours or shorter, and still more preferably 1 hour or longer and 15 hours or shorter.

By carrying out the reaction in the above range, the ratio of the presence of the resin component represented by the formula (1) in the varnish, and the ratio of the presence of the resin component represented by the formula (1) and the structure represented by the formula (9) can be adjusted. .

The varnish of the present invention can be suitably used to form an organic insulating layer in the manufacture of a multilayer printed circuit board and a package substrate. The varnish of the present invention can be applied to a circuit board to form an insulating layer, and industrially, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg.

[2] Prepreg, with resin film, metal foil laminated board, printed circuit board:

In the resin film of the present invention, the varnish of the present invention is coated on a support film, and the solvent in the varnish is volatilized by drying to be semi-cured (B-staged) to form a resin composition layer. Further, a protective film may be appropriately provided on the resin composition layer.

In addition, it is preferable that the semi-hardened state is a range in which the adhesion between the resin composition layer and the substrate on which the conductor wiring is formed is ensured when the varnish is cured, and the embedding property (fluidity) of the substrate on which the conductor wiring is formed is ensured. The scope.

The coating method (coater) can use a die coater, a comma coater, a bar coater, a kiss coater, and a roll coater. A roll coater or the like is suitably used depending on the thickness of the resin film. The drying method may use heating or hot air spraying or the like.

The drying conditions are not particularly limited, and drying is carried out so that the content of the organic solvent of the resin composition layer is usually 10% by weight or less, preferably 5% by weight or less. It is also different depending on the amount of the organic solvent in the varnish and the boiling point of the organic solvent. For example, the varnish containing 30 wt% to 60 wt% of the organic solvent is dried at 50 ° C to 150 ° C for about 3 minutes to 10 minutes. A resin composition layer is formed. The drying conditions are preferably such that appropriate drying conditions are appropriately set in advance by a simple experiment.

The thickness of the resin composition layer formed in the resin film is usually set to be equal to or greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is preferably 5 μm to 70 μm, and is preferably 3 μm to 50 μm, and more preferably 5 μm to 30 μm, in order to reduce the thickness and thickness of the printed circuit board. Therefore, the thickness of the resin composition layer is preferably 5% or more thicker than the thickness of such a conductor layer.

The support film of the present invention may, for example, be a polyolefin such as polyethylene, polypropylene or polyvinyl chloride, or polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") or polyethylene naphthalate. Examples of the film formed of a polyester, a polycarbonate, a polyimide, or the like include a metal foil such as a release paper, a copper foil, or an aluminum foil.

Further, the support film and the protective film to be described later may be subjected to unevenness treatment, corona treatment, and mold release treatment.

The thickness of the support film is not particularly limited, but is preferably 10 μm to 150 μm, more preferably 25 μm to 50 μm. It is also possible to laminate a protective film based on the support film on the surface of the resin composition layer which is not in contact with the support film.

The thickness of the protective film is not particularly limited and is, for example, 1 μm to 40 μm. By laminating the protective film, foreign matter can be prevented from entering. The resin film can also be taken up in rolls and stored.

In the embodiment of the method for producing the printed circuit board (multilayer printed wiring board) of the present invention with the resin film of the present invention, for example, a resin film is bonded to one or both sides of the circuit board by using a vacuum laminator. can.

Examples of the substrate used for the circuit board include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate.

Here, the circuit board herein refers to a circuit board in which a conductor wiring (circuit) is formed on one surface or both surfaces of the substrate as described above. Further, in a multilayer printed wiring board in which a conductor layer and a resin composition layer are alternately laminated, a circuit board in which a single surface or both surfaces of a multilayer printed circuit board is a conductor wiring (circuit) is also included in the circuit board. In the circuit board. The surface of the conductor wiring layer may be subjected to a roughening treatment in advance by a blackening treatment or the like.

Further, when a conductor layer is formed on at least one surface of a resin film, it is a metal foil-clad laminate.

In the above-mentioned bonding, when the protective film is provided with the resin film, the protective film is removed, and the resin film and the circuit substrate are pre-heated as needed, and the resin film is pressed and heated while being crimped. On the circuit board. In the present invention, a method of bonding to a circuit board under reduced pressure by vacuum bonding is suitably used.

The bonding conditions are not particularly limited. For example, the crimping temperature (bonding temperature) is preferably set to 70 ° C to 140 ° C, and the crimping pressure is preferably set to 0.1 MPa to 1.1 MPa. The bonding was carried out under reduced pressure of 20 mmHg (26.7 hPa) or less. Further, the bonding method may be a batch type or a continuous type using a roll.

After bonding the resin film to the circuit board, it is cooled to near room temperature, peeled off when the support film is peeled off, and thermally cured, whereby a resin composition layer can be formed on the circuit board. The heat curing conditions are appropriately selected depending on the type and content of the resin component in the resin composition, and are preferably selected from the range of 150 ° C to 220 ° C for 20 minutes to 180 minutes, more preferably 160 ° C to 200 ° Choose within °C, 30 minutes to 120 minutes.

After the resin composition layer was formed, when the support film was not peeled off before curing, peeling was performed here. Then, a hole is formed in the resin composition layer formed on the circuit board as needed, and a via hole and a through hole are formed. The opening may be, for example, a known method such as drilling, laser, plasma, or the like, and may be performed by combining the methods as needed. The opening of a laser using a carbon dioxide laser or a YAG laser is the most common. method.

Next, a conductor layer is formed on the resin composition layer by dry plating or wet plating. For dry plating, a known method such as vapor deposition, sputtering, ion plating, or the like can be used. In the case of wet plating, first, an oxidizing agent such as permanganate (potassium permanganate or sodium permanganate), dichromate, ozone, hydrogen peroxide/sulfuric acid, nitric acid or the like is used to harden the resin. The surface of the composition layer is roughened to form a convex and concave anchor. As the oxidizing agent, an aqueous sodium hydroxide solution (alkaline permanganic acid aqueous solution) such as potassium permanganate or sodium permanganate can be preferably used. Then, a conductor layer is formed by a method of combining electroless plating and electroplating. Further, a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method of forming the subsequent conductor wiring, for example, a known subtractive process, a semi-additive process, or the like can be used.

The prepreg of the present invention is produced by impregnating the varnish of the present invention into a sheet-like reinforcing substrate made of fibers by a solvent method or the like, and then heating to be B-staged. That is, a prepreg in which the varnish of the present invention is impregnated into a sheet-like reinforcing substrate formed of fibers can be obtained.

As the sheet-like reinforcing substrate formed of the fibers, for example, a well-known sheet-like reinforcing substrate used in various laminated sheets for electrical insulating materials can be used. Examples of the material thereof include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimine, polyester, and polytetrafluoroethylene, and mixtures of the fibers. .

The substrates have shapes such as woven fabric, non-woven fabric, roving, chopped strand mat, and surfacing mat, and the materials and shapes thereof are selected according to the use or properties of the target molded article. , can be used alone or in combination of two or more materials and shapes as needed. The thickness of the substrate is not particularly limited, and for example, about 0.03 mm to 0.5 mm can be used. In terms of heat resistance, moisture resistance, and processability, a substrate surface-treated with a decane coupling agent or the like is suitable. A substrate that has been fiber-opened by mechanical means.

The solvent method is a method in which a sheet-like reinforcing substrate is immersed in the varnish of the present invention, the varnish is impregnated into the sheet-like reinforcing substrate, and then dried.

Then, a method of manufacturing a multilayer printed wiring board using the prepreg manufactured as described above is, for example, superimposing one sheet of the prepreg of the present invention on a circuit board or overlapping a plurality of sheets as needed, and interposing the release film The metal plate was clamped and laminated under pressure and heating. The pressurization and heating conditions are preferably carried out at a pressure of 0.5 Mpa to 4 Mpa and a temperature of 120 ° C to 200 ° C for 20 minutes to 100 minutes. Further, similarly to the resin film, the prepreg may be bonded to the circuit board by vacuum bonding, and then heat-hardened. Thereafter, the surface of the cured prepreg is roughened in the same manner as described above, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.

Instance

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the examples.

Example 1

In a four-port separable flask equipped with a thermometer, a condenser, and a stirring device, an indoline type epoxy resin (trade name: YX-8800, manufactured by Nippon Epoxy Resin Co., Ltd., epoxy equivalent: 174 to 183) was charged. 200 g, benzoguanamine (manufactured by Nippon Shokubai Co., Ltd.), which is a compound having an amine group, 13.8 g, a cresol novolak resin as a compound having a phenolic hydroxyl group (trade name: KA-1165, Dainippon ink) Manufactured by Chemical Industry Co., Ltd., hydroxyl equivalent: 119) 13.2 g, and 170.2 g of propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) as a solvent, and stirred under heating at 140 °C. After confirming that the material was dissolved, further heating was carried out for 10 minutes, and then 1 g of varnish was taken, and polystyrene conversion was determined using a high performance liquid chromatography (manufactured by Tosoh Co., Ltd., TSK-gel G-3000H). The weight average molecular weight before the reaction. After maintaining the reaction at 140 ° C for 5 hours, 1 g of a varnish was taken, and a weight average molecular weight in terms of polystyrene was determined using a high performance liquid chromatography. Then, 92.0 g of cresol novolak resin (KA-1165, manufactured by Dainippon Ink and Chemicals Co., Ltd.) was added, and the mixture was heated and dissolved at 100 ° C for 30 minutes to prepare a varnish.

1 ml of the varnish produced was taken, and it was confirmed by the particle size meter that the particle|grains which have the particle diameter of 5 micrometers or more were carried out, and it was carried out at 5 degreeC, and the time of the precipitation of the material from the varnish was visually confirmed. When the precipitation of the material was confirmed, 1 ml of the varnish was taken, and the presence or absence of particles having a particle diameter of 5 μm or more was examined using a granulometer, and the time until the particles of 5 μm or more were confirmed was determined as the storage time.

Example 2

Benzeneamine (manufactured by Nippon Shokubai Co., Ltd.) was changed to 27.6 g, and cresol novolak resin (KA-1165, trade name manufactured by Dainippon Ink and Chemicals Co., Ltd.) was changed to 22.6 g, propylene glycol monomethyl Ethyl acetate (manufactured by Kanto Chemical Co., Ltd.) was changed to 162.8 g, and cresol novolak resin (KA-1165, trade name manufactured by Dainippon Ink Chemical Industry Co., Ltd.) added after the reaction was changed to 56.3 g. Otherwise, a varnish was produced in the same manner as in Example 1, and the storage time was obtained.

Example 3

A cresol novolac resin which is a compound having a phenolic hydroxyl group (trade name: KA-1165, Dainippon Ink Chemical Industry Co., Ltd.) is 4.6 g of melamine (manufactured by Kanto Chemical Co., Ltd.) as a compound having an amine group. (manufactured) is a cresol novolak resin (KA-1165, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), which is made up of 176.2 g of propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.). A varnish was produced in the same manner as in Example 1 except that the amount was 46.0 g, and the storage time was determined.

Example 4

The dicyandiamine (manufactured by Kanto Chemical Co., Ltd.), which is an amine group-containing compound, was changed to 11.6 g, and propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) as a solvent was changed to 118.8 g. In the same manner as in Example 1, except that the additional cresol novolak resin (KA-1165, trade name manufactured by Dainippon Ink and Chemicals Co., Ltd.) was changed to 65.8 g and the reaction time at 140 ° C was changed to 3 hours. Varnish, and find the storage time.

Example 5

The dicyandiamide (manufactured by Kanto Chemical Co., Ltd.) was changed to 2.4 g, and the cresol novolak resin (trade name: KA-1165, manufactured by Dainippon Ink and Chemicals Co., Ltd.) was changed to 26.2 g, propylene glycol monomethyl ether. The acetic acid ester (manufactured by Kanto Chemical Co., Ltd.) was changed to 137.4 g, and the cresol novolak resin (KA-1165, manufactured by Dainippon Ink and Chemicals Co., Ltd.) added after the reaction was changed to 46.0 g. A varnish was produced in the same manner as in Example 1, and the storage time was obtained.

Example 6

The epoxy resin was changed to 200 g of naphthol novolak type epoxy resin (trade name: ESN-175, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent: 254), and dicyandiamide (manufactured by Kanto Chemical Co., Ltd.) was changed to 3.3 g, phenol novolak resin (trade name: TD-2090, manufactured by Dainippon Ink and Chemicals Co., Ltd., hydroxyl equivalent: 105) as a compound having a phenolic hydroxyl group was changed to 24.8 g, propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) was changed to 115.5 g, and the phenol novolak resin (TD-2090, trade name manufactured by Dainippon Ink and Chemicals Co., Ltd.) added after the reaction was changed to 41.3 g, and the storage time was changed at 140 °C. A varnish was produced in the same manner as in Example 1 except for the above, and the storage time was determined.

Example 7

As the epoxy resin, a biphenol novolak type epoxy resin (trade name: NC-3000-H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 284 to 294) 76.8 is used in addition to the indoline type epoxy resin. g, and an aminotriazine novolak (trade name: LA3018-50P, manufactured by DIC Co., Ltd., 50% solution) as a compound having an amine group is 62.6 g, and a cresol novolac as a compound having a phenolic hydroxyl group The varnish resin (trade name: KA-1165, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) is 14.8 g, propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) is 230.5 g, and cresol novolac is added after the reaction. A varnish was prepared in the same manner as in Example 1 except that the varnish resin (KA-1165, manufactured by Dainippon Ink and Chemicals Co., Ltd.) was 124.9 g, the reaction temperature was 120 ° C, and the holding time was 14 hours. Custody time.

Example 8

As the epoxy resin, a biphenol novolak type epoxy resin (trade name: NC-3000-H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 284 to 294) 76.8 is used in addition to the indoline type epoxy resin. g, a cresol novolak resin (trade name: KA-1165, large Japan) which is 3.8 g of a compound having a phenolic hydroxyl group as a compound having an amine group (manufactured by Kanto Chemical Co., Ltd.) (Ink Chemical Industry Co., Ltd.) is 18.1 g, propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) is 113.0 g, and cresol novolak resin is added after the reaction (KA-1165, Dainippon Ink Chemical Industry) A varnish was prepared in the same manner as in Example 1 except that the product name of the company was 124.9 g and the propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) was 115.1 g, and the storage time was determined.

Example 9

As the epoxy resin, a biphenol novolak type epoxy resin (trade name: NC-3000-H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 284 to 294) 200.5 is used in addition to the indoline type epoxy resin. g, and a cresol novolak resin (trade name: KA-1165, Japan) which is 3.9 g of a compound having a phenolic hydroxyl group as a compound having an amine group (manufactured by Kanto Chemical Co., Ltd.) Manufactured by Ink Chemical Industry Co., Ltd., which is 197.2 g, propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.), 161.6 g, and added propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) A varnish was produced in the same manner as in Example 1 except that the amount was 164.7 g. Make and find the storage time.

Comparative example 1

Into a four-neck separable flask equipped with a thermometer, a condenser, and a stirring device, 200 g of an indoline-type epoxy resin (trade name: YX-8800, manufactured by Nippon Epoxy Resin Co., Ltd.) was introduced as an amine group. Benzoamine (manufactured by Nippon Shokubai Co., Ltd.) of the compound, 13.8 g, cresol novolac resin (KA-1165, trade name manufactured by Dainippon Ink and Chemicals Co., Ltd.) as a compound having a phenolic hydroxyl group 105.2 g. 170.2 g of propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) as a solvent, which was heated and dissolved at 140 ° C to prepare a varnish.

1 ml of the varnish produced was taken, and it was confirmed by the particle size meter that the particle|grains which have the particle diameter of 5 micrometers or more were carried out, and it was carried out at 5 degreeC, and the time of the precipitation of the material from the varnish was visually confirmed. When the precipitation of the material was confirmed, 1 ml of the varnish was taken, and the presence or absence of particles having a particle diameter of 5 μm or more was examined using a granulometer, and the time until the particles of 5 μm or more were confirmed was determined as the storage time.

Comparative example 2

Benzeneamine (manufactured by Nippon Shokubai Co., Ltd.) was changed to 27.6 g, and cresol novolac resin (KA-1165, trade name manufactured by Dainippon Ink Chemical Industry Co., Ltd.) was changed to 78.9 g, propylene glycol monomethyl ether A varnish was produced in the same manner as in Comparative Example 1, except that the acetate (manufactured by Kanto Chemical Co., Ltd.) was changed to 162.8 g, and the storage time was determined.

Comparative example 3

The melamine (manufactured by Kanto Chemical Co., Ltd.), which is a compound having an amine group, was changed to 4.6 g, and the cresol novolak resin (KA-1165, trade name manufactured by Dainippon Ink and Chemicals Co., Ltd.) was changed to 72.2 g. A varnish was prepared in the same manner as in Comparative Example 1, except that the propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) was changed to 172.2 g, and the storage time was determined.

Comparative example 4

Changed dicyandiamide (manufactured by Kanto Chemical Co., Ltd.) to 11.6 g, cresol novolak resin (KA-1165, trade name manufactured by Dainippon Ink and Chemicals Co., Ltd.) to 65.8 g, propylene glycol as a solvent A varnish was produced in the same manner as in Comparative Example 1, except that the monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) was changed to 118.8 g, and the storage time was determined.

Comparative Example 5

The dicyandiamine (manufactured by Kanto Chemical Co., Ltd.), which is a compound having an amine group, was changed to 2.4 g, and the cresol novolak resin (KA-1165, trade name manufactured by Dainippon Ink and Chemicals Co., Ltd.) was changed to A varnish was prepared in the same manner as in Comparative Example 1 except that 72.2 g of propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) was changed to 137.4 g, and the storage time was determined.

Comparative Example 6

The epoxy resin was changed to 200 g of a naphthol novolak type epoxy resin (ESN-175, trade name, manufactured by Tohto Kasei Co., Ltd.), and dicyandiamide (manufactured by Kanto Chemical Co., Ltd.) which is a compound having an amine group was changed. A phenol novolak resin (TD-2090, manufactured by Dainippon Ink and Chemicals Co., Ltd.), which is a compound having a phenolic hydroxyl group, was changed to 65.0 g, propylene glycol monomethyl ether acetate (Kantong Chemical Co., Ltd.) A varnish was produced in the same manner as in Comparative Example 1, except that the production was changed to 115.5 g, and the storage time was determined.

Comparative Example 7

As the epoxy resin, a biphenol novolak type epoxy resin (trade name: NC-3000-H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 284 to 294) 76.8 is used in addition to the indoline type epoxy resin. g, and an aminotriazine novolak (trade name: LA3018-50P, manufactured by DIC Co., Ltd., 50% solution) as a compound having an amine group is 62.6 g, and a cresol novolac as a compound having a phenolic hydroxyl group The varnish resin (trade name: KA-1165, manufactured by Dainippon Ink and Chemicals Co., Ltd.) was 139.7 g, and propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) was 230.5 g, and other examples were compared with the comparative example. 1 A varnish was produced in the same manner, and the storage time was obtained.

Comparative Example 8

As the epoxy resin, a biphenol novolak type epoxy resin (trade name: NC-3000-H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 284 to 294) 76.8 is used in addition to the indoline type epoxy resin. g, a cresol novolak resin (trade name: KA-1165, large Japan) which is 3.8 g of a compound having a phenolic hydroxyl group as a compound having an amine group (manufactured by Kanto Chemical Co., Ltd.) A varnish was prepared in the same manner as in Comparative Example 1 except that 143.0 g of propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) was used as the storage time.

Comparative Example 9

As the epoxy resin, a biphenol novolak type epoxy resin (trade name: NC-3000-H, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 284 to 294) 200.5 is used in addition to the indoline type epoxy resin. g, and a cresol novolak resin (trade name: KA-1165, Japan) which is 3.9 g of a compound having a phenolic hydroxyl group as a compound having an amine group (manufactured by Kanto Chemical Co., Ltd.) A varnish was produced in the same manner as in Comparative Example 1, except that 197.2 g and propylene glycol monomethyl ether acetate (manufactured by Kanto Chemical Co., Ltd.) were 326.3 g. Make and find the storage time.

The weight average molecular weight and storage time measurement results of the varnish produced in the examples are shown in Table 1 below. In addition, the measurement results of the storage time of the varnish produced in the comparative example are shown in Table 2 below.

The storage time of Examples 1 to 6 in Table 1 was 168 hours or longer, that is, the storage time was 1 week or longer. On the other hand, the storage times of Comparative Examples 1 to 6 of Table 2 were as short as 2 hours to 5 hours. The epoxy resin containing a polycyclic structure shown in the examples and the comparative examples is called a crystalline epoxy resin, and has low solubility with respect to a solvent. Therefore, even if the temperature of the varnish is increased to the melting point or higher of the epoxy resin and melted, it is precipitated in a short time after returning to room temperature. On the other hand, in Examples 1 to 6, a part of the functional groups of the epoxy resin were reacted, whereby a storage time of 30 times or more of the comparative example was achieved even under storage conditions of 5 ° C. Therefore, it is understood that it is important to react a part of the functional groups of the epoxy resin having a polycyclic structure in terms of securing the storage time. Further, the varnish of the present example can improve the solubility unlike the prior varnish, and can stabilize the varnish and retain the varnish for a long period of time, so that the workability is excellent and the storage stability is high.

Further, the copper foil laminated board produced by using the varnish of the example has a low coefficient of thermal expansion, and it can be said that the occurrence of warpage which was previously regarded as a problem can be suppressed even when a printed circuit board is produced.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

10. . . Semiconductor wafer

12. . . Sealing material (semiconductor package)

14. . . Bonding lead

16. . . Semiconductor package substrate

18. . . Substrate

20. . . Through hole

twenty two. . . Solder ball

C. . . Crack due to warpage

FIG. 1 is an explanatory view showing a state of warpage of a semiconductor package of a PoP structure.

Figure 2 is a DSC curve for YX-8800 and dicyandiamide in an equivalent ratio of 1:1.

Claims (14)

A varnish which is a resin having a polycyclic structure having at least one epoxy group and containing at least one of a biphenol novolak structure, a naphthalene structure, a naphthol novolak structure, an anthracene structure, and an indoline structure. A part of the epoxy group and the amine having a compound having an amine group are obtained by a reaction in a solvent, and the weight average molecular weight of the resin component after the reaction is 800 or more and 4,000 or less. The varnish according to claim 1, wherein the phenolic hydroxyl group of a part of the epoxy group of the resin and the compound having a phenolic hydroxyl group is reacted in the solvent. The varnish according to claim 1 or 2, wherein the compound having an amine group is any one of decylamine, dicyandiamide and an aminotriazine novolak. A varnish which is a resin having a polycyclic structure having at least one epoxy group and containing at least one of a biphenol novolak structure, a naphthalene structure, a naphthol novolak structure, an anthracene structure, and an indoline structure. A part of the epoxy group is obtained by reacting the phenolic hydroxyl group of the compound having a phenolic hydroxyl group in a solvent, and the weight average molecular weight of the resin component after the reaction is 800 or more and 4,000 or less. The varnish according to claim 2, wherein the compound having a phenolic hydroxyl group is a phenol novolak resin or a cresol novolak resin. The varnish according to claim 1 or 4, wherein the resin has a structure selected from the group consisting of a naphthalene structure, a biphenyl aldehyde varnish structure, a ruthenium structure, At least one of the groups consisting of indoline structures. The varnish according to claim 1, which contains a resin component having a structure represented by the following formula (1), (In the above formula, R ¹ is a residue of a compound having an amine group). The varnish according to the seventh aspect of the invention, wherein the total ratio of the respective structures of the structure represented by the above formula (1) and the structure represented by the following formula (2) is represented by the above formula (1) The existence ratio of the structure is 40% or less. A prepreg formed by applying a varnish as described in claim 1 or 4 to a substrate and heating and drying the varnish. The prepreg according to claim 9, wherein the substrate is a glass woven fabric, a glass non-woven fabric, an aromatic polyamide woven fabric or an aromatic polyamide woven nonwoven fabric. A resin film formed by applying a varnish as described in claim 1 or 4 to a film and heating and drying it. A metal foil-clad laminate which is as claimed in the patent application The prepreg according to item 9 has a conductor layer on at least one side. A metal foil-clad laminate having a conductor layer on at least one side of a resin film as described in claim 11 of the patent application. A printed circuit board formed by wiring the conductor layer provided on at least one surface of a metal foil-clad laminate according to claim 12 or 13.